Liquid hydrocarbon lubricant, an additive therefor, and a process of making the additive



Patented June 13, 1950 LIQUID HYDROCARBON LUBRICANT, AN AD- DITIVE THEREFOR, AND A PROCESS OF MAKING THE ADDITIVE Mayer B. Goren, Brighton, Mara, and David E.

Adelson, Berkeley, Calif aasignors to Shell Development Company, San Francisco, corporation of Delaware No Drawing. Application Serial No. 160.9

Calif. a

July 14, 1947, :s

13 Claims. (CL 252-321!) This invention relates to new and novel products which have properties of greatly improving and stabilizing lubricants. More particularly, this invention pertains to oleaginous materials, especially lubricants, such as mineral lubricating oils, synthetic lubricants of hydrocarbon and non-hydrocarbon origin and the like, containing a multi-functional additive having detergent and anti-ringsticking properties, as well as acting as an inhibitor of oxidation and corrosion.

It is well known that various lubricants, whether doped or undoped, tend to oxidize and form corrosive bodies and sludge when used in modern engines and machines operating under ordinary conditions, and especially at high speeds, elevated temperatures, heavy loads and other adverse conditions. Also as lubricants deteriorate during use, hard carbonaceous materials are formed on ensine and machine parts, causing scratching and scuffing of movable metal parts and sticking of valves and piston rings in engines. In addition, known lubricants are generally incapable of maintaining a continuous lubricating film between movable metal parts; this results in a gradual or rapid wearing away of the metal parts. The damage thus caused requires replacement of such parts, or even a complete overhauling of engines and machines. resulting in expensive loss of production and time. I

In the case of the highest quality non-corrosive, stable undoped mineral lubricating oils, which are highly refined for specific uses, or synengines, and the like. These additives serve a very important function because by modifying this carbonaceous material so that it can be removed easily, the tendency of engine parts to become stuck is inhibited; ring sticking, Piston scuillng and scratching and wearing away of other parts and material reduction of engine emciency is thereby prevented.

Other additives have been developed which act as detergents in order to assist in the removal of soot, sludge, varnish, and/or lacquer formed from deterioration of the oil at high operating temperatures. Detergents, due to their cleansing action, prevent the build-up of these deleterious materials and assist in removing those formed.

Anti-wear additives have the property of reducing friction of movable metal parts of the same or different metals. Due to the function exerted or property imparted by such additives on lubricents, wear caused by direct frictional contact of metals can be greatly reduced. Also additives have been developed for withstanding extreme pressures, dispersion of impurities. solubilizing of certain other additives, etc.

The large number of additives thus developed has been due to the fact that an additive is capable of functioning mainly in only one specific manner: very few lubricant additives have the ability of improving a lubricant in more than just one respect. Thus a good anti-oxidant might not be able to inhibit lacquer and varnish formation I on piston rods, or to act as a detergent or corrothetio lubricants developed for special uses, it has been found that such oils and lubricants are generally highly susceptible to oxidation and deterioration, becoming progressively more and more corrosive in en ines and machines even under ordinaryoperating conditions. i To improve the lubricating properties of 01 and synthetic lubricants, it has become the practice to blend therewith one or more additives which have the effect or the property of inhibiting deterioration of lubricants and impart to them certain beneficial properties. Thus additives have been specifically designed which have the property of inhibiting corrosion of alloyed bear.- ings such as copper-lead, cadmium-silver and the like, developed for automotive, Diesel and aircraft engines. Acidic oxidation or decomposition components formed in lubricants during use can readily attack these hearings, but are inhibited or prevented from doing this by the formation of a corrosion protective film formed with theaid of the additive on the bearing surface. Additives have also been developed which possess the property of modifying the carbonaceous materials 7 formed by deterioration of lubricants on piston rods, rings and valves and other metal parts in.

sion inhibitor. In many cases, it is found that whereas an additive possesses very good properties in one respect, this same additive is the cause of harmful deposits in another respect. A second and third additive is therefore frequently required in order-to obtain a good stable lubricant. The combination of additives in lubricants wherein each additive exerts its influence without interfering with the function of other additives present is a difllcult matter to attain because in most cases additives co-react or interfere with each other. To prevent this from occurring great care mustbe taken in selecting the additives, mixing them in specific proportions, and continuously watching and replacing additives which have stopped functioning or have deteriorated.

It is an object of this invention to improve the properties of various oleaginous materials. Another object is to add to compounded or doped lubricants a multi-functional material whereby a synergistic effect is produced, resulting in a product of accentuated and improved properties. Another object of this invention is to add to mineral lubricating oils, synthetic lubricants, and the like, a multifunctional material so as to inhibit oxidation and corrosion and prevent the formation of sludge, varnish and lacquer in said lubricants even under adverse operating conditions. Still another object of this invention is to use in lubricating compositions a material which prevents ring-sticking as well as the sticking of other engine parts due to deterioration of the lubricant. Also it is an object of this invention to use in lubricating compositions a material which inhibits wear, scuiilng, scratching and other damage to engine parts. It is-still another object of this invention to provide novel compounds which possess multifunctional improving and enhancing properties when added to lubricants.

The above and other objects may be obtained in accordance with the present invention by adding to oleaginous materials, e. g. various lubricating bases, 9. minor amount of salts of reaction product obtained by treating phosphorus sulfide with saturated and unsaturated cyclic ke tone fractions having at least 12 and preferably more than 18 carbon atoms in themolecule, said ketone fractions having been derived from isophorone bottoms during its synthesis from acetone by condensation as well as from other sources and thereafter treating said reaction product with a metal or organic base. Preferably, the phosphorus sulfides used to produce the reaction products of this invention should be selected from the class consisting of phosphorus pentasulfide, phosphorus heptasulfide and the like. The preferred ketones used to obtain the oil additive of this invention are the unsaturated cyclic ketones which are reacted with these phosphorus sulfides and are normally obtained from isophorone bottoms produced by condensation of acetone under elevated temperature and pressure. The isophorone bottoms thus produced may be fractionated into various cuts each of which may be used to react with phosphorus sulfide to form the compound or oil additive of this invention. Among the specific isophorone fractions which may be used to form the reaction product of this invention are topped crude isophorone, topped crude hydrolyzed isophorone bottoms, and the like. Although the mol ratio of the phosphorus sulfide and unsaturated cyclic ketone of this invention may be varied over wide limits, it is preferable to keep them within the range of from 1:2 to 1:12, respectively. The reaction between these two ingredients is generally carried out under controlled elevated temperature conditions. This reaction product may be treated with any suitable metal such as the alkali metals, alkaline earth metals, heavy metals, nitrogen containing organic bases and the like. Specifically such a compound as a hydroxide, carbonate or oxide of Na, Li, K, Ca, Ba, Sr, Mg, Al, Zn, Cu, Cr, Cd, Fe, Mn, Ni, Sn etc. or basic reagents such as ammonia alkyl or aryl substituted ammonia such as amines and the like.

The terms topped crude isophorone bottoms and topped crude hydrolyzed isophorone bottoms, and similar terms, which will be hereinafter used and fully described are generic and are used to identify various unsaturated cyclic ketone fractions of relatively high molecular weight obtained from acetone condensation. Unsaturated cyclic ketone fractions useable in reactions of the kind under consideration may be obtained by condensing acetone in 30% to 60% caustic solution at a temperature ranging between about 130 and 170 C., and under pressure of from 300 to 500 pounds per square inch. The resultant product is preferably subjected to distillation to remove distillable ketones and other constituents and impurities. The productfl clohexene-2-one-l, an unsaturated cyclic ketone containing only nine carbon atoms in the molecule. Isophorone bottoms produced by condensation of acetone under conditions referred to above includes within its scope any and all unsaturated cyclic ketones containing at least 12 and preferably more than 18 carbon atoms and having generally the chemical structural configuration of isophorone as well as the chemical structural configuration resulting from its condensation.

Crude isophorone bottoms can be fractionated and/or chemically treated and each fraction thereof can in turn be treated with phosphorus sulfide at elevated temperatures to produce a compound containing both phosphorus and sulfur. Among the various fractions which can be obtained from crude isophorone bottoms are topped crude isophorone bottoms which contain at least 15 carbon atoms in the molecular and which are obtained after removal of distillate from crude isophorone bottoms to a still head temperature of 140 (2., at 10 mm. Hg pressure. Crude isophorone bottoms can be subjected to hydrolysis with dilute sodium hydroxide and the acetone and isophorone formed removed by distillation. The bottoms can then be filtered and purified and comprise essentially unsaturated cyclic ketones containing at least 12 and more carbon atoms in the molecule and are referred to as crude hydrolyzed isophorone bottoms. This material can be subjected to distillation to split it into two fractions. The distilled hydrolyzed isophrone fraction has a boiling point of about 140 C. at 10 mm. Mg pressure and consists of a mixture of unsaturated cyclic ketones containing between 15 to 18 carbon atoms in the molecule. The residue is referred to as topped crude hydrolyzed isophorone bottoms and is similar to topped crude isophorone bottoms. They comprise essentially unsaturated-cyclic ketones of at least 15 carbon atoms in the molecule. Crude isophorone bottoms can be also subjected to condensation over solid sodium hydroxide to yield two types of resinous materials. The first resinous fraction 'or soft resin has a viscosity at 210; F. of about 25-26 centistokes and an average molecular weight of 320 to 350. The heavier fraction or medium resin has a viscosity at 210 F. of about to centistokes and an average molecular weight of 370 to 390. All of the various unsaturated cyclic ketone fractions obtained in the manner fully described above can be used for reacting with phosphorous sulfide to form a multi-functional lubricating additive. Other cyclic ketones having at least 12 carbon atoms are obtained by hydrogenating the above unsaturated cyclic ketones to obtain saturated cyclic ketones having at least 12 carbon atoms, alkyl cyclohexanone, i. e. dibutyl cyclohexanone, alkyl substituted carvomenthone, menthone, pulegone, carvone, camphor, and the like having at least 12 carbon atoms.

Phosphorus sulfides generally can be used in i I producing reaction products of thisinvention and preferably phosphorus pentasulfide and phosphorus heptasulfidc are used of their availability, cost and desired reactivity. The exact manner in which phosphorus and sulfur enter the reaction is at present not known or understood and the chemical structure of the reaction is also not known; however, it might be possible that thioketones containing phosphorus in the form of ester linkages are produced when phosphorus sulfide is reacted with unsaturated cyclic ketones. This is in contrast to early references of reactions of the type under discussion which stated that phosphorus did not enter the reaction and the products formed were thioketones. Thus A. E. Kretov and Ya P. Komissarov in the Jr. Gen.

Chem. U. S. S. R. 5388-91 (1935), state that the action of phosphorus pentasulfide on aliphatic ketones results in the formation of thioketones. Gatterman in Ber. 28, 2877 disclosed that when -benzophenone in benzine solution is heated with phosphorus pentasulfide for several hours at 130 C. in a bomb, thiobenzophenone forms and phosphorus does not enter into the I reaction. Also Patents 2,309,829 and 2,402,640 disclose that ketones when reacted with phosphorus'sulflde results in the formation of thioketones and phosphorus does not enter into the reaction. Unlike any previous teachings reaction'products of this invention contain both phosphorus and sulfur, and physically as well as chemically are quite unlike in properties to thioketones.

The phosphorus sulfide-unsaturated'cyclic ketone reaction products of this invention can be prepared from any of. the ketone fractions obtained in the manner described above, although certain fractions are preferred to others. The kind of phosphorus sulfide used, the ratio of the two reactants, the temperature, time and conditions under which the reaction is carried out, as well as the manner in which the final product is recovered, are also important and controlling factors. The preferred ketone fractions are topped crude isophorone bottoms which are residues remaining after removal of distillate from crude isophorone bottoms to a still head temperature of 140 C. at mm. Hg. pressure, and comprise unsaturated cyclic ketones containing at least carbon atoms in the molecule. Another preferred fraction is topped crude hydrolyzed isophorone bottoms obtained from crude hydrolyzed isophorone bottoms similar to the topped crude isophorne bottoms. The term "topped used throughout has the same meaning as in the petroleum art, namely, a distillation or fractionation step, whereby certain materials are removed as an overhead fraction.

Phosphorus pentasulfide and phosphorus heptasulfide are preferred although other phosphorus sulfides can be used. The moi ratio of phosphorus sulfide to ketone is a most important factor in obtaining a desired reaction product. when the moi ratio of phosphorus sulfide to ketone is from 1:2 to 1:1.2, superior reaction prodnets are obtained. However, this mol ratio need not be adhered to strictly and may be varied at times to 1:4 and even 1:8 of phosphorus sulfide to ketone, respectively. Generally, when these ratios are used the resultant products are relatively inferior and for some lubricants may prove to be unsatisfactory.

The reaction temperature can be varied between about 130' C. and about 200" C. or higher, and preferably between 150' C. and 170"- C. Howimately. steam temperature.

e; be controlled quite carefully and be. restricted within relatively rather narrow limits. to obtain a desired controlled reaction. If initially the reaction is allowed to progress at a rapid rate over 100 C., due to the vigor of the resultant reaction, it cannot then be controlled and an undesirable product forms. The initial stage of'the reaction should be carefully controlled andheated-slowly in a suitable bath or by anysuitabl'emeans to an initial temperature of between about .0. and C., and thereafter heated relatively more rapidly to the desired or optimumtemperature.

The reaction should be carried out in substantially inert atmosphere and the two materials can be reacted per se or dispersed in a suitable inert or non-reactive diluent and then reacted under conditions described above. When the. reaction is completed, the desired fraotioncanbe extracted with a suitable material, such as non-aromatic hydrocarbons, e. g. one having a boiling range of between 164 F. to 233 F., or an aviationbase stock gasoline boiling up to 190 F1 and containing little, e. g. not more than about 4%. aro-' matics.

Thegeneral procedure for preparing the salts of reaction products obtained bytreating phosphorus sulfide-cyclic ketones may be attained by' dispersing or dissolving a" phosphorus sulfide treated cyclic ketone" in a large quantity of a suitable hydrocarbon oil by heating to approx- To this, composi tion a calculated amount of neutralizing agents" such as lime or the like, is added and the mixture agitated at an elevated temperature of above about C. for over a period of 2 hours. After'the' reaction is completed a stream of inert gas is introduced to remove any entrained moisture or other contaminants. The neutralized phosphorus sulfide-cyclic ketone reaction product is then filtered to recover the product from the oil-and may be refiltered to. remove excess lime' and other impurities. 4

The preparation of salts of phosphorus-sulfide with saturated or unsaturatedcyclic ketone reaction products of this invention is relatively simple and requires no elaborate or special equipment, undue precautions or skill. The obtainment of the desired reaction products simply requires a mixing and stirring of unsaturated cyclic ketones of this invention withfor example dry, powdered phosphorus pentasulfide, in an inert atmosphere, such as nitrogen or carbon dioxide, for 2 to 8 hours. Initially, the reaction is kept at between about 60 C. and about 80 C., the mixture being then rapidly heated to an elevated temperature of 200 0., or higher. At the completion of the reaction the desired fraction may be extracted with a non-aromatic hydrocarbon having a boiling point of 164 F. to 233 F. The nonextractable material is discarded and the solution is filtered, evaporated at steam temperature in a current of inert gas to yield the desired products which when treated'with a metal or organic base are suitable as lubricant additives. The additives thus produced vary in color from amber to dark brown and in consistency from viscous liquid to brittle solids. They are readily soluble in various petroleum lubricating oils as well as other types of oleaginous materials, oils and synthetic lubricating bases.

To more clearly illustrate the present invention, the following examples are presented. It is to be understood, however, that various modiever, the initial or starting temperature should fications can be restored without departing from 7 the spirit of the invention as presented in the subioined claims. 4

Example I A mixture of cyclic unsaturated ketones con- The reaction products of this invention can be used as valuable additives to or constituents of heavy duty oils, motor oils, diesel oils, aviation oils, synthetic oils, and the like, because of taining at least 18 carbon atoms in the molecule, Q their anti-corrosion, mmat and u. obtained by t pp g bottom! from crude wear properties. The amount of additive used ph r ne b m a a kettle temperature of can be varied over relatively wide limits but sen- 140' 0.. and mm. H8 pressure 9110891101118 eraliy it is not necessary to use more than 5% pentasulfide in the mol ratio of 8.2. respectively. by weight of'the reaction product nnd preferably were stirred and beam in all inert atmosphere 1. only b tw b t 0 1 t 29 by u I of carbon dioxide for approximately five hours to m t base lubricant mum about The mm m Placed The reaction product of this invention can be initially in a bath mllntelwl at about, combined with other additives in lubricants, tartar... ti hltttszrtsm- M w g- 3,": W rove essure extracted with mn'ammauc hydro anti-fogming asent, and the li h e. Among the carbon having a boiling range of between about specific additives which can be used are undo-h 164. and The solutmn altered and uble detergents which include oil-soluble salts the filtrate evaporated at steam temperature in of various bases with detergenuformmg acid a current of carbon dioxide. Theresultant 10 such bases include metal as we m fi ggg contained 143% sulfur?! bases. Metallic bases include the hydrocides, etc. of the alkali metals, Cu, Mg, Ca, Sr, Ba, Zn, sem wls vt' s disso ig gfi fi Sn, Pb, Cr, Mn, Fe, Ni, Co, etc. Organic amount of mineral lubricating ,oil by gentle 28 m fi z fg j g gggfiwm heating at about C. to C. Ifdesired.this Eu of deter ant forming acids th mixture may be filtered to remove any foreign mp es 8 m 9 d u m1 me matter To this heated mhb various fatty acids of, say, 10 to 30 carbon atoms, :3 g of lm'le is added and a minor wool fat acids, parailln wax acids (produced by amount of water and the product heated for :0 oxidation of a chlorilimted fatty about two to three hours at about 100 C. The rosin ac aroma c 9 mixture is the muted to remove excess nme cluding aromatic fatty acids, aromatic hydro and the filtrate reheated for about two hours at acids paramn wax mic acldsbetween a and A stream or alkyl salicylic acids, phthalic acid monoesters, m as is then blow through the mixture to 35 aromatic keto acids, aromatic ether acids; demon entrained foreign matter moisture and phenols as di-(alkyl phenol) sulfides and di-sulthe The salt can be movelied by any sun-P fides, methylene bis alkyl phenols: sulionic acids able means from the oil solution. The calcium such as may be Produced by treatment of m salt of this reaction product contains both sulm hydrocarbons or high boilins Petroleum il fur and phosphorus and is .readfly soluble in m with sulfuric acid; sulfuric acid mono-esters; mine"; n phosphoric, arsonic and antimony acid mono sam le If and di-esters. including the corresponding thio- The 1mm mtiom namely ,cycuc mt phosphoric, arsenic and antimony acids; phosh h rated ketones-phosphorus pentasulfide reaction, 45 p g g fi i g ggf gtg fi g: i earth rfi g i fga fit m m gg g xgf phosphate di-esters. including the thiophosphate N 1! tamed. at respectively dl-cster; the alkaline earth diphenolates, specifion analysis this product k 3 cally the calcium and barium salts of 'diphenoi and 4.6% phosphorus. The calcium salt of this so mono and poly sumdes' reaction product was formed in the manner de- Nmmletamc detergents mum! scribed in Example L such as the phosphatides such as lecithin and Compositions of this invention were subjected cepholin, ertain fatty 011 as rapeseed 0 1 vol oto oxygen absorption t t and thrust bearing lized fatty or mineral oils and the like. rosion test, the results of which are self-explanas An excellent metallic detergent'for the present atory and are listed in the table. The thrust p r se is t e calcium-salt of oi l p tmbearing corrosion test is described in the Naleum sulfonic acids. This maybe present advantionalPetroleum News, September 17, 1941, pp. tageously in the amount ofabout 0.025% to 3-294-296. 0.2% sulfate ash. Also alkaline metal salts of Oxidation absorption test I Catalyst: 1 cm Culg. oil m Adam". Amount 1 600 ml. Corrosiorl Sulfate bxygen Ash Time Percent Hanna 0 C. us 1 Non 2 Pifl treatodunsatnlatedcyclicketoneoontahiing iiimrbonatoms 0.1 14;2 170 pared in a lo I o. 02 36. s 170 2 ifiiifiimfiS$333i%fi3$3mns$t m 0.03 90.0 170 l A refined, undoped lubricating oil, having a viscosity oi 64-64 S. U. at 210 F. was employed, oxidation at O.

I Estimated approximated critical corrosion temperature All oxidation products corrected to ory m absorbed.

to 1,600 mi. oxygen abiorbedllm 3. oil, assuming amount of product is proportioned alkyl phenol-aldehyde condensation:

Anti-oxidants comprise several types, for example, alkyl phenols. such as 2,4,6 'tr irnethyl phenol, penta methyl-phenol,.2,4 dimethyl-6- tertiary-butyl phenol, 2,4-dimethyl-6-octyl phe-J no], 2,6-ditertiary-butyl-4-methyl-phenol, 2,4,6 tritertlary-butyl phenol and the-like; amino phenols as benzyl amino phenols; amines suchas dibutyl phenylene diamine, diphenyl amine, phenyl-beta-naphthylamine' phenyl-alphamaphthylamine, dinaphthylamine.

Corrosion, inhibitors or anti-rusting compounds may also be present, such as dicarboxylic acids of 16 and more carbon atoms: alkali metal and alkaline earth salts of sulfonic acids and fatty acids; organic compounds containing an acidic radical in close proximity to a nitrile, nitro or nitroso group (e. g. alpha cyano stearic acid) Extreme pressure agents which maybe-used comprise: esters of phosphorus acids such as triaryl, alkyl hydroxy aryl, or aralkyl phosphates, thiophosphates or phosphites and the like; neutral aromatic sulfur compounds of relatively high boiling temperatures such as diaryl sulfides, diaryl disulfides, alkyl aryl disulfides, e. g. diphenyl sulfide, diphenol sulfide. dicresol sulfide, dixylenol sulfide, methyl butyl diphenoljsulfide, dibenzyl sulfide, corresponding diand tri-sulfides, and the like; sulfurized fatty oils or esters of fatty acids and monohydric alcohols, e. g. sperm oil, jojoba oil, etc.; in which the sulfur is strongly bonded; sulfurized long chain 'olefins such as may be obtained by dehydrogenation or cracking of wax; sulfurized phosphorized fatty oils or acids, phosphorus acid esters having sulfurized organic radicals, such as esters of phosphoric or phosphorus acids with sulfurized hydroxy fatty acids; chlorinated hydrocarbons such as chlorinated paraffin, aromatic hydrocarbons, terpenes, mineral lubricating oil, etc.; or chlorinated esters of fatty acids containing the chlorine in position other than alpha position.

Additional ingredients may comprise oil-soluble urea or thio-urea derivatives, e. g. urethane's,

allophanates, carbazides, carbazones, etc.; polyisobutylene polymers, unsaturated polymerized esters of fatty acids and monohydric alcohols and other high molecular weight oil-soluble compounds.

Depending upon the additive used and condi-- tions under which it is used, the amount of additive used mayv vary from 0.01% to 2% or higher. However, substantial improvement is obtained by usin amounts ranging from 0.1% to 0.5% in combination with phosphorus sulfide-unsaturated cyclic ketone reaction products of this invention.

It is to be understood that while the features of the invention have been described and illustrated in connection with certain specific examples, the invention, however, is not to be limited thereto or otherwise restricted, except by the prior art and the scope of the appended claims.

We claim as our invention:

1. A composition comprising a major amount of a lubricating liquid hydrocarbon and a minor amount sufficient to stabilize said lubricating liqud hydrocarbon against deterioration and improve its anti-wear properties of a stable, noncorrosive neutralized phosphorus and sulfur containing reaction product obtained by reacting at a temperature ranging from 130' C. to about 200 C. a phosphorus sulfide with an unsaturated cyclic ketone fraction having at least 12 carbon atoms and being' an' isophorone bottoms residual fraction having a minimumboiling point greater than 140 .C. at 10mm. Hg" pressure, and derived from condensation of acetone to higher molecuular weight isophorone type fraction, the ratio .of the phosphorus'sulfide to the ketone compound being 1:4 to about-1:8,.respectively, and neutralizing the reaction product witha basic reagent. 5

' 2. A composition comprising a maioramount of a'lubricating liquid hydrocrabonand "a minor jamount sunlcient to stabilize said lubricating liquid hydrocarbonagainst deterioration and improve its' anti-wear properties of a stable, noncorrosive neutralized phosphorus and sulfur containing reaction product obtained by reacting 'ata temperature ranging from 130 C, to about 200C. a phosphorus sulfide with an unsaturated cyclic ketone fraction having atleast 12 carbon atoms .andbeing an isophorone bottoms residual'fraction having a minimum boiling point greater than 140 .C; at 10 mm, Hg pressure, and derived from condensation of I acetone to higher molecular weight isophorone type fractions. the ratio of the phosphorus sulfide to the ketone compound being 1:4 toabout 1:8 respectively, and neutralizing the reaction product "with a basic. reagent containing an alkali metal constituent.

3. A composition comprising a major amount of a lubricating liquid hydrocarbon and a minor .amount'sufiicient to stabilize said lubricating cyclic ketone fraction having at least 12 carbon atoms and being an isophorone bottoms residual fraction having a minimum boiling point greater than 140 C. at 10 mm. Hg pressure, and derived from condensation of acetone to higher molecular weight isophorone type fractions, the ratio pound being 1:4 to about 1:8, respectively, and

of the phosphorus sulfide to the ketone comneutralizing the reaction product with a basic reagent containing an alkaline earth metal constituent.

4. A composition comprising a major amount of a lubricating liquid hydrocarbon and a minor amount sufiicient to stabilize said lubricating liquid hydrocarbon against deterioration and imcyclic ketone fraction havin at least 12 carbon atoms and being an isophorone bottoms residual fraction having a minimum boiling point greater than 140 C.- at 10 mm. Hg pressure, and derived from condensation of acetone to higher molecular weight isophorone type fractions, the ratio of the phosphorus sulfide to the ketone compound being 124 to about 1:8, respectively, and neutralizing the reaction product with a basic reagent containing a heavy metal constituent.

5. A lubricant comprising a major amount of mineral lubricating oil and a minor amount sufilcient to stabilize said mineral oil against deterioration and improve its anti-wear properties of a stable non-corrosive phosphorus and sulfur containing reaction product obtained by reactms at a temperature of from C. to 200 C.

- P osphorus pentasulnde with unsaturated cyclic ketone fractions having at least 12 carbon atoms and being sin isophorone bottoms residual fraction having a minimum boiling point greater than 140 C. at mm. Hg pressure and derived from the condensation of acetone, the ratio of the phosphorus pentasulfide to the ketone compound being 1:4 to about 1:8, respectively, and neutralizing the reaction product with a basic reagent;

6. A lubricant comprising a major amount of mineral lubricating oil and a minor amount sumcient to stabilize said mineral oil against deterioration and improve its anti-wear properties of a stable non-corrosive phosphorus and sulfur containing reaction product obtained by reacting at a temperature of from 120 C. to 200 C. phosphorus pentasuliide with isophorone bottoms comprising essentially unsaturated cyclic ketone fractions having at least 12 carbon atoms in the molecule, the ratio of the phosphorus pentasulflde to the ketone compound being 1:4 to about 1:8, respectively, and neutralizing the reaction product with a basic reagent.

'1. A lubricant comprising a major amount of mineral lubricating oil and a minor amount sumcient to stabilize said mineral oil against deterioration and improve its anti-wear properties of a stable, non-corrosive phosphorus and sulfur containing reaction product obtained by reacting at a temperature of from 130 C. to 200 C. phosphorus pentasuliide with unsaturated cyclic ketone fractions. having at least 12 and more carbon atoms and derived from the condensation of acetone and being an. isophorone bottoms residual fraction having a minimum boiling point greater than 140' C. at 10 mm. Hg pressure, the ratio of the phosphorus pentasuifide to the ketone compound being 1:4 to about 1:8, respectively,

and neutralizing the reaction product with a 40 basic reagent, containing sodium as a metal constituent thereof.

8. A lubricant comprising a major amount of mineral lubricating oil and a minor amount sumcient to stabilize said mineral oil against deterioration and improve its anti-wear properties of a stable, non-corrosive phosphorus and sulfur containing reaction product obtained by reacting at a temperature of from 130 C. to 200 C. phosphorus pentasulflde with unsaturated cyclic ketone fractions having=at least 12 and more carbon atoms and derived from the condensation of acetone-and being an isophorone bottoms residual fraction having a minimum boiling point a eater than 140' C. at 10 mm. Hg pressure, the ratio of the phosphorus pentasuliide to the ketone compound being 1:4 to about 1:8, respectively, and neutralizing the reaction product with a basic reagent, containing calcium as a metal constituent thereof.

9. A lubricant comprising a major amount of mineral lubricating oil and a minor amount suflicient to stabilize said mineral oil against deterioration and improve its anti-wear pr rties of a stable, non-corrosive phosphorus and sulfur containing reaction product obtained by reacting at a temperature of from 130 C. to 200 C. phos- 1 12' phorus pentasulnde with unsaturated cvclickeione fractions having at least-:12 and more carbon atoms and derived from thefcondensation of acetone and being an isophorone bottoms residual fraction having a minimum boiling point greater than 140' C. at 10 mm. Hg pressure. the ratio of the phosphorus to the ketone compound being 1:4 to about" 1:8, respectively, and neutralizing the reaction product with a basic reagent, containing aluminum as a metal constituent thereof.

7 10. A process of producing a stable, non-cor- "rosive phosphorus and sulfur containing reaction product which comprises reacting at a temperature of from C. to 200' C. a phosphorus sulfide at an elevated temperature with an unsaturated cyclic ketone fraction which is an isophorone bottoms residual fraction having a minimum boiling point greater than C. at 10 mm. Hg pressure and having at least 12 carbon atoms and derived from condensation of acetone to higher molecular weight isophorone type fraction until about 1.2% to 4.6% phosphorus and 14.3 to 15.3% sulfur have entered the reaction product and neutralizing the reaction product with a basic reagent.

11. A process of producing a stable, non-corrosive, oil-soluble product, which comprises reacting at a temperature of from 120' C. to 200 C.-

one mole of Pass with from 1.2 to 2 moles of an unsaturated cyclic ketone fraction which is an isophorone bottoms residual fraction having a minimum boiling point greater than 140' C. at

10 mm. Hg pressure and having at least 12 carbon atoms until about 1.2% to 4.6% phosphorus and 14.3 to 15.3% sulfur have-entered the reaction product and neutralizing the reaction product with a basic reagent containing calcium as a metal constituent thereof.

12. As a composition, a neutralized phosphorus I and sulfur containing unsaturated cyclic ketone having at least 12 carbon atoms and derived from the condensation of acetone, the phosphorus and sulfur content being 1.2 to 4.6% and 14.3 to 15.3%, respectively produced by the process of claim 10.

13. As a composition, a neutralized phosphorus and sulfur containing unsaturated cyclic ketone having at least 12 carbon atoms, the phosphorus and sulfur being 1.2 to 4.6% and 14.3 to 15.3%,

the process of claim 11. MAYER B. GOREN. DAVID E. ADELSON.

REFERENCES CITED The following references are of record in the file of this patent:

' UNITED STATES PATENTS respectively produced by Number 7 Name Date 2,242,260 Prutton May 20, 1941 2,329,436 Cook Sept. 14, 1943 2,368,000 Cook Jan. 23, 1945 2,383,498 Otto et aL Aug. 28. 1945 2,383,510 Redman et a1. Aug. 28, 1945 2,419,153 Musselman Apr. 15, 1947 2,419,325 Musselman Apr. 27, 1947 

1. A COMPOSITION COMPRISING A MAJOR AMOUNT OF A LUBRICATING LIQUID HYDROCARBON AND A MINOR AMOUNT SUFFICIENT TO STABILIZE SAID LUBRICATING LIQUID HYDROCARBON AGAINST DETERIORATION AND IMPROVE ITS ANTI-WEEAR PROPERTIES OF A STABLE, NONCORROSIVE NEUTRALIZED PHOSPHORUS AND SULFUR CONTAINING REACTION PRODUCT OBTAINED BY REACTING AT A TEMPERATURE RANGING FROM 130*C. TO ABOUT 200*C. A PHOSPHORUS SULFIDE WITH AN UNSATURATED CYCLIC KETONE FRACITON HAVING AT LEAST 12 CARBON ATOMS AND BEING AN ISOPHRONE BOTTOMS RESIDUAL FRACTION HAVING A MINIMUM BOILING POINT GREATER THAN 140*C. AT 10 MM. HG PRESSURE, AND DERIVED FROM CONDENSATION OF ACETONE TO HIGHER MOLECUULAR WEIGHT ISOPHORONE TYPE FRACTION, THE RATIO OF THE PHOSPHORUS SULFIDE TO THE KETONE COMPOUND BEING 1:4 TO ABOUT 1:8, RESPECTIVELY, AND NEUTRALIZING THE REACTION PRODUCT WITH A BASIC REAGENT.
 11. A PROCESS OF PRODUCING A STABLE, NON-CORROSIVE, OIL-SOLUBLE PRODUCT, WHICH COMPRISES REACTING AT A TEMPERATURE OF FROM 120*C. TO 200*C. ONE MOLE OF P2S5 WITH FROM 1.2 TO 2 MOLES OF AN UNSATURATED CYCLIC KETONE FRACTION WHICH IS AN ISOPHORONE BOTTOMS RESIDUAL FRACTION HAVING A MINIMUM BOILING POINT GREATER THAN 140*C. AT 10 MM. HG PRESSURE AND HAVING AT LEAST 12 CARBON ATOMS UNTIL ABOUT 1.2% TO 4.6% PHOSPHORUS AND 14.3 TO 15.3% SULFUR HAVE ENTERED THE REACTION PRODUCT AND NETURALIZING THE REACTION PRODUCT WITH A BASIC REAGENT CONTAINING CALCIUM AS A METAL CONSTITUTENT THEREOF.
 13. AS A COMPOSITION A NEUTRALIZED PHOSPHORUS AND SULFUR CONTAINING UNSATURATED CYCLIC KETONE HAVING AT LEAST 12 CARBON ATOMS, THE PHOSPHORUS AND SULFUR BEING 1.2 TO 4.6% AND 14.3 TO 15.3%, RESPECTIVELY PRODUCED BY THE PROCESS OF CLAIM
 11. 